You are on page 1of 30

ISSN 1995-0780, Nanotechnologies in Russia, 2008, Vol. 3, Nos. 5–6, pp. 242–271. © Pleiades Publishing, Ltd., 2008.

Original Russian Text © P.A. Troshin, R.N. Lyubovskaya, V.F. Razumov, 2008, published in Rossiiskie nanotekhnologii, 2008, Vol. 3, Nos. 5–6.

REVIEWS

Organic Solar Cells: Structure, Materials, Critical Characteristics, and Outlook
P. A. Troshin*, R. N. Lyubovskaya, and V. F. Razumov
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia *e-mail: troshin@cat.icp. ac.ru
Received December 25, 2007

Abstract–This review surveys recent advances in the field of photovoltaic devices based on organic photoactive materials and used for converting solar energy into electricity. Different architectures of organic photovoltaic devices are considered: bilayer, bulk heterojunction, and tandem cells. Major groups of organic semiconductors are described together with some numerical data on their performance in solar cells. Possible ways of improving the efficiency of organic solar cells are discussed. The bibliography consists of 80 references. DOI: 10.1134/S1995078008050029

INTRODUCTION The finite supply of traditional fossil fuels (oil, natural gas, coal, etc.) underscores the urgency of searching for alternative energy sources. Nowadays the most important role is attributed to solar energetics. The power of energy resources worldwide is estimated at 20 TW. The solar power delivered to the Earth is ~105 TW. Solar energy is converted into electricity by means of solar cells. At present, solar cells are mainly based on inorganic semiconducting materials, crystalline and amorphous silicon being the most important among them. Silicon solar cells have been known for more than half a century. Power conversion efficiencies in silicon cells are as high as 20%, and their service life is more than 25 years. The cost of silicon itself is low. However, silicon solar cells are not widely used thus far. The reason is that silicon photovoltaic technology is very complex, resulting in high cost of silicon solar cells. In the United States and Europe, the current cost of 1 kW/h of energy provided by solar cells is about $ 0.30. This is two to five times higher than the cost of 1 kW/h of energy delivered to the population from traditional sources (thermal and nuclear power plants). The best estimates are that costs of energy from inorganic solar cells will level off to $ 0.10 per kW/h in 2014. Taking into account that energy is becoming a strategic resource, many countries are investing in the development of national solar cell facilities. Among these countries, Japan, Germany, and the United States rank first, second, and third, respectively, in total production volume [2]. Actually, the use of silicon solar cells is justified only in those few cases when the customer is remote from other energy sources. For example, this solves the problem of power supply to lighthouses, mountain ski lodges, distant farms, etc.

At present, organic solar cells are being extensively studied worldwide since they have the potential to inexpensively produce electricity from solar energy. According to calculations, 1 kW/h of electricity produced by organic solar cells should cost $ 0.01–0.02 [3]. The low cost of organic cells is due to their simple and inexpensive production technology. Organic semiconductors are usually soluble in organic solvents, which makes it possible to produce liquid inks and apply them by printing them to flexible polymeric substrates. This technique has been thoroughly developed and used by numerous Western companies. Flexibility is another important advantage of organic solar cells. Classical electronics is dominated by the use of rigid and brittle structures, which is determined by the physical properties of inorganic materials. Organic semiconductors yield flexible and plastic films, which is an important advantage of this class of materials. Such cells can be integrated into clothing, facial coatings, packaging, etc. They can be rolled up into compact cylinders, which are easy to transport and can be unrolled when necessary. They can be used as compact power sources, for example, for recharging the batteries of mobile devices. The outlook for organic photovoltaics is good. Solar power conversion efficiencies up to 6.5% have been achieved in tandem organic solar cells. Organic solar cells with an efficiency of 5.1% have already been certified at the independent photovoltaic cell standardization center. Programs for commercialization of organic solar cells are being developed by giant corporations, such as Siemens and Sharp, as well as by specialized companies, for example, Konarka Technologies, Inc. However, organic photovoltaics is still at the research stage. This review surveys the basic results of such

242

ORGANIC SOLAR CELLS

243

Cathode Acceptor Donor PEDOT:PSS ITO anode Substrate

Cathode Donor-acceptor blend PEDOT:PSS ITO anode Substrate

Fig. 1. Schematic layout of a typical bilayer photovoltaic cell (left) and bulk heterojunction cell.

hv

LUMO LUMO HOMO Donor Donor HOMO Acceptor Donor* Acceptor Acceptor

Fig. 2. Scheme illustrating the work of an organic photovoltaic device. Illumination results in photoinduced charge separation between the donor and acceptor components followed by their migration to electrodes.

studies. A great number of publications dealing with organic solar cells appear every year. Some of them have already been systematized in several earlier reviews [4–9]. Therefore, here we do not intend to consider in detail the data obtained in each of the numerous publications on organic photovoltaics; rather, we will focus on the most fundamental results, with the emphasis on those published in 2005–2007 that were not included in previous reviews. ARCHITECTURE OF ORGANIC PHOTOVOLTAIC CELLS AND THEIR OPERATION Nearly all described configurations of organic photovoltaic cells can be divided into two groups: bilayer cells, in which layers of photoactive components are deposited over one another; and bulk heterojunction cells, in which the donor and acceptor are blended in a single photoactive layer (Fig. 1). These types of cells differ not only in structure, but also in materials and manufacturing processes; we discuss this below. In cells of both types, light induces electron transfer from the donor to the acceptor (charge separation, Fig. 2). In bilayer cells, this process occurs at the donor–accepNANOTECHNOLOGIES IN RUSSIA Vol. 3 Nos. 5–6

tor interface. In bulk heterojunction cells, charge separation occurs throughout the bulk of the active layer where the donor and acceptor are in contact. Once charge separation has occurred, the challenge is to prevent the reverse process, recombination, and deliver the charges to different electrodes. In bilayer cells, electrons can move to an electrode in the layer of the acceptor material (n-type material) and positive charges, holes, can move in the layer of the donor material (p-type material). The probability that charge carriers will return to the interface or will wander into the other layer and recombine is rather small, which is an advantage of bilayer cells (Fig. 3). In bulk heterojunction cells, transport of charge carriers to the electrodes and suppression of recombination are possible only if the donor and acceptor phases are completely ordered. This can be envisioned as the existence of interpenetrating three-dimensional networks of donor and acceptor materials in the active layer (Fig. 3). An organic solar cell is characterized by its current– voltage curve, which is measured under standard AM1.5 illumination conditions. To do this, a solar simulator is used. The standard light power density is 100 mW/cm2.
2008

244 (a) –

TROSHIN et al. (b) –

+

+

Fig. 3. Schematic representation of charge transport to electrodes in (a) bilayer cells and (b) the bulk heterojunction cell.

I, mA/cm2 14 12 10 8 6 4 2 0 –2 –4 Imax –6 Isc –8 –10 –0.3 –0.2 –0.1 0 0.1 0.2 V, V 0.3 0.4 0.5 0.6 0.7 Vmax Voc FF = (ImaxVmax)/(IscVoc)

Fig. 4. Typical current–voltage curve of a photovoltaic cell.

From the light current–voltage characteristics, three basic parameters of a photovoltaic cell can be determined: open circuit voltage (Voc), short circuit current (Isc), and fill factor (FF). Figure 4 shows a typical current–voltage curve of a photovoltaic cell. The short-circuit current density (Isc) is determined at zero applied voltage. The voltage that should be applied to compensate for the emf of the cell (i.e., to bring the current to zero) is referred to as the open circuit voltage (Voc). If the coordinates (current and voltage) of every point of the curve in the fourth quadrant are multiplied, this product will be maximal in magnitude at some point. This point is referred to as the maximal energy point and determines the actual efficiency of a photovoltaic cell. The current and voltage at this point are designated as I = Imax and V = Vmax. The

power conversion efficiency of a photovoltaic cell (η) is calculated by the formulas η% = ( P el /P light ) × 100 = [ ( I max V max )/P light ] × 100 = [ ( I sc V oc FF )/P light ] × 100, (1)

where Plight is the power of the incident light from an external source, Pel is the electric power provided by the photovoltaic cell, and FF is the proportionality coefficient called the fill factor. Graphically, the fill factor is the ratio of the area of the rectangle with sides Imax and Vmax (smaller) to the area of the rectangle with sides Isc and Voc (larger). Below we consider basic advances in the field of organic photovoitaics separately for bilayer and bulk heterojunction cells and survey the factor that influence the efficiency of organic photovoltaic dells.
Vol. 3 Nos. 5–6 2008

NANOTECHNOLOGIES IN RUSSIA

Sn(II)).6% [17. the introduction into the C60/CuPc system of the extra layer of tin phthalocyanine. however. 5). the efficiency of cells based on a combination of these materials has not increased substantially. later these results were not reproduced [11]. The most important advantage of pyrrolidinofullerenes containinig pyridyl groups is their ability to form complexes with zinc phthalocyanine at the interface between the donor and acceptor layers (Fig. the achieved power conversion efficiency was only 2. due to a decrease in the short-circuit current density. Zn. in the bilayer p–n system metal phthalocyanine (p-type)/perylene derivative (n-type) (Fig. In particular. This complex formation enhances the efficiency of charge separation in the donor–acceptor system. With the aim of further increasing the efficiency of bilayer cells. Therefore. these groups of materials are considered separately. (2) the perylene compound PTCBI. Indeed. to increase the open circuit voltage. As a result. should lead to an increase in the photocurrent.1%. 5.6% was achieved for the C60/copper phthalocyanine (CuPc) system. which absorbs in the NANOTECHNOLOGIES IN RUSSIA Vol. Tang. Power conversion efficiencies of 2. 3 Nos. At the same time. and the maximal efficiency of devices of this type was ~1. and (3) fullerene C60. C. Zn) are the most reliable [12]. used by C. determined by X-ray crystallography [16]. boron subphthalocyanine was used as the donor material instead of copper phthalocyanine [14]. other materials have been studied. A disadvantage of these compounds is the existence of organic groups. The structure of one of them. 2008 . many works dealing with the photovoltaic properties of systems of the phthalocyanine/perylene derivative type have been published. however. In addition. Some researchers claimed that a power conversion efficiency of about 3.0% [13]. Molecular formulas of (1) metal phthalocyanines (M = Cu. These compounds are highly soluble in organic solvents.5% achieved from C60/MPc) systems (M = Cu. Tang created first high-efficiency organic light emitting diodes and showed in 1986 that. Since then. Considerable progress has been made with the use of fullerene C60 as the acceptor material in combination with metal phthalocyanines in solar cells. MATERIALS USED IN PHOTOVOLTAIC CELLS The structures and properties of materials used in bilayer cells and bulk heterojunction cells are rather different. Similar complexes of pyrrolidinofullerenes were isolated with zinc-containing porphyrins.W. its organic derivatives—pyrrolidinofullerenes containing chelating pyridyl groups—have been used as n-type materials. however. photoinduced charge separation makes it possible to convert light into electricity with a power conversion efficiency of about 1% [10]. the expectations of researchers were not met. A subsequent. 6c. which makes it possible to fabricate films from solution by spin coating. 18]. Bilayer Cells Bilayer cells were historically the first photovoltaic cells that showed an acceptable power conversion efficiency of about 1%. Instead of nonmodified fullerene C60.0–2. Deposition of a film from a solution is considerably a more economic and efficient process than vapor deposition. 6b).0% [15]. which considerably impair the electron transport properties of fullerenes. 5–6 red and infrared regions.ORGANIC SOLAR CELLS 245 N N N N N N N O 1 2 N O N M N N N 3 Fig. the maximal power conversion efficiency achieved for pyrrolidinofullerene/ZnPc cells is 1. However. Tang in 1980–1987 modeled p–n junctions based on organic semiconductors. the open circuit voltage in this system was twice as large as in the C60/CuPc system. is shown in Fig. more careful optimization of the photovoltaic cell based on boron subphthalocyanine and C60 provided a power conversion efficiency of about 3.

In both compounds in Fig. hence. A recent promising approach consists in combining a bilayer cell and a bulk heterojunction cell into one multicomponent solar cell [18]. it is expected that they will be comparable with the correVol. the architecture of multicomponent cells is suitable for obtaining power conversion efficiencies as high as 7%.246 TROSHIN et al. The molecular structure of oligothiophene is shown in Fig. 8b) [20]. thus resulting in efficient photoinduced charge separation at the layer interface. As a voltage slightly above 3. the fill factor and. In these cells. 6b. It is likely that the most promising strategy for increasing the performance of bilayer cells implies the replacement of metal phthalocyanines with other organic donors. light emission at 660 nm with a bandwidth less than 150 nm (pure red color) is observed. charges are generated both at the interface between the phthalocyanine layer and the bulk heterojunction layer (electron transfer from phthalocyanine to a fullerene compound) and in the bulk heterojunction layer (electron transfer from a polymer to a fullerene compound). At nearly the same time as the report on the use of an oligothiophene donor in solar cells in combination with C60. In a multicomponent photovoltaic cell. when a fullerene derivative containing chelating groups (pyrrolidinofullerene PyF) is mixed with nonchelating fullerene derivatives of the PCBM type. N N N Cl B N N N (a) N N N N N N N Zn N N N N N7 N1 N3 N2 N4 N N5 N6 Zn (b) (c) Fig. as in common bilayer cells (Fig. 28%. It was recently shown that a bilayer cell based on combination of fullerene with an oligoth- iophene electron-donor material provides a power conversion efficiency up to 3. which is comparable with the best polymer–compound systems (see below). However.4%. 3 Nos.0 V is applied. there is intramolecular charge transfer from the donor tris[4-(2-thienyl)phenyl]amine or pentathiophene system to electron-deficient dicyanovinyl moieties.85% due to the low fill factor. 7). Its specific feature is that it contains donor thiophene and acceptor dicyanovinyl moieties. 5–6 2008 NANOTECHNOLOGIES IN RUSSIA . Intramolecular charge transfer leads to an extension of the absorption spectrum of materials up to 700 nm. The power conversion efficiency for the compound shown in Fig. the power conversion efficiency can be increased twofold by careful optimization of the layer deposition technology. 6. namely. Although the voltage–brightness characteristics and conversion efficiency for LEDs were not reported in [20]. The best performance of these devices is achieved when a blend of fullerene compounds is used. Multicomponent photovoltaic cells convert light in the range 350–850 nm. Potentially. PyF forms complexes with ZnPc. another work was published in which a similar material was used: it was a substituted triphenylamine containing both thiophene and dicyanovinyl moieties (Fig. a zinc phthalocyanine film is coated with a bulk heterojunction layer—a blend of fullerene compounds and a polyconjugated polymer—rather than with an acceptor layer. Therefore. which seems to be a record value for bilayer solar cells [19]. According to our estimates. 8. As shown in Fig. Molecular formulas of (a) boron subphthalocyanine and (b) trisubstituted pyrrolidinofullerene (PyF) forming a complex with zinc phthalocyanine and (c) the structure of the coordination complex of pyrrolidinofullerene and zinc tetraphenylporphyrin as determined by X-ray crystallography [16]. 8b in combination with fullerene C60 (bilayer cells) was only 1. further optimization of charge transport in this complex system is required. the use of this material in photovoltaic cells ensures light conversion in a wide spectral range. The most interesting feature of photovoltaic cells based on this material is that they can operate as light-emitting diodes with excellent characteristics. 8a.

It is impracticable to improve this efficiency since it is close to the theoretical maximum for the [60]PCBM/MDMO-PPV system. the polymer matrix (MDMO-PPV) is shown in yellow. For many years. (a) Scheme of layers in a multicomponent photovoltaic cell. (b) Illustration of the processes of photoinduced charge separation and transport to electrodes. This leads to a nearly 100% quantum efficiency of photoinduced charge separation in the bulk heterojunction layer. as a rule. This is 2008 . Deposition from solution makes it possible to reduce expenses in producing devices with the use of modern printing technologies (ink-jet printing etc. Currently. the contact area between the donor and acceptor phases is generally many orders of magnitude larger than in bilayer cells. Other combinations of materials have also been studied. where [60]PCBM is a cyclopropane derivative of C60 and MDMO-PPV is a substituted p-phenylenevinylene (Fig. readily soluble in organic solvents and can be applied from solution. 5–6 and polyconjugated polymers (p-type).0% [21]. 10) [6]. The only interesting exception is the recently described system based on benzocoronene and perylenediimide (Fig. 7. the best materials for organic bulk heterojunction solar cells are fullerene compounds (n-type) NANOTECHNOLOGIES IN RUSSIA Vol. however. this is because the materials used for their manufacture are. achieved only in cells with fullerene compounds. sponding characteristics of the best materials used in manufacturing red organic LEDs.6%. (c) Molecular formulas of the materials. The layer of zinc phthalocyanine (ZnPc) is shown in blue. Bulk Heterojunction Cells Organic photovoltaic cells in which the active layer is a mixture of donor and acceptor materials are currently the focus of intense research. as a rule.).5–2.ORGANIC SOLAR CELLS (a) – LiF/Al (0. and gray spheres correspond to the phase of fullerene compounds (PCBM + PyF). in the bulk heterojunction cell. 9). 3 Nos. The maximal power conversion efficiency for this system is 2. high power conversion efficiencies are. First. which are vertically segregated in the active layer of the cell and thereby provide excellent morphology. Second.6/100 nm) (PCBM + PyF)/ MDMO-PPV (80–100 nm) ZnPc (45 m) PEDOT:PSS (60 nm) ITO (200 nm) Substrate + (c) (b) 247 N N N N N O * O O CH3 * O MDMO-PPV ZnPc N N N N N Zn N N PyF PCBM Fig. The conversion efficiency for monochromatic light with a wavelength of 490 nm in these cells was about 2. all model organic solar cells were based on the [60]PCBM/MDMO-PPV system. which was achieved through careful optimization of all production parameters for these cells [22].

3 Nos. The basic advantage of P3HT over MDMO-PPV is the broader absorption spectrum (almost to 700 nm) in films. An increase in film thickness to 230 nm can lead C12H25 C12H25 C12H25 O N O C12H25 C12H25 O N O C12H25 Fig. (Left) benzocoronene and (right) perylenediimide compounds used as materials in photovoltaic cells. 8. [70]PCBM. However. Molecular formulas of new organic materials of pthe P3HT/PCBM system [27. S NC In such stacks. Some authors have claimed a power efficiency of 5. The improved transport properties of N P3HT as compared with MDMO-PPV are important for obtaining high current densities in photovoltaic cells.5% CN is the theoretical maximum [25. which makes it possible to obtain current denS sities in cells up to 11–12 mA/cm2. poly(3NC hexylthiophene) (P3HT) [24]. 26] have shown that these values are clearly overestimated.5 mA/cm2 at a film thickness of less than 170 nm was observed when the acceptor material based on (the thickness of the active layer in cells is generally no fullerene C60 was replaced by the analogous C70 com. S S The next step in the development of organic photoCN voltaics was the use of regioregular poly(3-alkylthiophene)s as donor materials. which Theoretical studies dealing with optical modeling of prevents the open circuit voltage (Voc) in the cells from absorption. These structures are composed of stacks of polymer chains. detailed further studies [25. An important advantage (b) of P3HT is its self-organization in films at elevated temS peratures to form so-called laminar structures. in particular. reflection.0%. The narrow spectral effects in thin films based on P3HT and PCBM (Fig.more than 100 nm) [29]. The optimal thickness is about pound. 26]. the hole mobility is very high (up to CN 10–2 cm2/(V s)). the use of [70]PCBM Bu Bu Bu Bu NC CN CN led to better light absorption in the active layer. 5–6 2008 . wider visible absorption spectrum as compared to analogous C60 derivatives. more type containing thiophene and dicyanovinyl fragments. which NC entailed an increase in power conversion efficiency S S S to 3. Therefore.248 (a) TROSHIN et al. 11) range in which the given material combination absorbs have shown that the maximal current density that can (350–600 nm) does not allow us to obtain photocurrent be achieved in a P3HT/PCBM-based cell is about densities higher than 5–6 mA/cm2. The maximal power CN efficiency of optimized devices based on P3HT/PCBM is slightly above 4. transmission. and an efficiency of about 4. 9. 28]. NANOTECHNOLOGIES IN RUSSIA Vol. Some improvement 11. Fullerene C70 compounds have a 70 nm.0% or even higher in Fig. limited by the electronic levels of the materials.0% [23]. and interference being increased above 900 mV.

3 Nos. A noteworthy result was recently obtained for the polymer PF10TBT: the power conversion efficiency in the cells is 4. new fullerene derivatives are also synthesized for use in photovoltaic cells instead of PCBM. all obtained fullerene-containing materials are still inferior to metanofullerenes [60]PCBM and [70]PCBM. which is higher than in the cells with P3HT [30]. The efficiencies of photovoltaic devices based on PCBM-type fullerenes and different donor polymers are summarized in Table 1.5 illumination should be considered overestimated. Therefore. The data on some of such polymers are presented in Table 2.2 to 5. Molecular formulas of materials most frequently used for bulk heterojunction cells.5% [31]. another team achieved an efficiency of only about 3. the absorption edge should be above 700 nm. These polymers are referred to as low bandgap polymers. The increase in the power efficiency from 3. 2008 .2%. this will hardly lead to higher power conversion efficiencies since the open circuit voltage and fill factor decrease rapidly with increasing thickness. However. Further enhancement of the performance of solar cells requires the development of donor polymers absorbing in an even longer wavelength range than P3HT. Select results for different fullerene derivatives are compiled in Table 3. It was shown that alkanedithiol additions affect the morphology of the active layer of a cell and presumably afford optimal phase separation of the donor polymer and acceptor fullerene compound. The polymer PCPDTBT is the best to date: in combination with [70]PCBM. However. i. Somewhat earlier. There are still very few donor polymers giving acceptable power conversion efficiencies in photovoltaic cells. all those data in Table 1 where the current density for the P3HT/PCBM system exceeds 11.. 5–6 alkanedithiols as cosolvents for film application.5% is caused by the use of NANOTECHNOLOGIES IN RUSSIA Vol.e. 12. 10. Almost all of them are copolymers containing fluorene and benzothiadiazole fragments. There are a large number of polyconjugated polymers that provide power conversion efficiencies lower than 1.5 mA/cm2 under 100 mW/cm2 AM1. In addition to the synthesis of new polymers.ORGANIC SOLAR CELLS 249 O O CH3 [60]PCBM O [70]PCBM O CH3 O * * O MDMO-PPV * S S * P3HT Fig. it provided a power conversion efficiency of about 5. Their molecular formulas are shown in Fig.2% with the same polymer [32]. Such polymers should have a bandgap (the energy difference between the LUMO and HOMO) of less than 2 eV.5% in photovoltaic devices. to a certain increase in the short-circuit current density.

Short-circuit current density as a function of film thickness (taken from [29]). Some experimental results of the authors are shown by asterisks. presumably due to losses at the photoactive layer–electrode interfaces.9–1. CdSe. 13) [68]. the difference between the work functions is 0.5 –1. and then hybrid photovoltaics can become a real competitor to organic photovoltaics based on the use of fullerene-containing materials and polyconjugated polymers. the method of their stabilization in solution. Voc(max) = EA(LUMO) – ED(HOMO). semiconductor nanocrystals. Below we consider factors that have an effect on each of them.1 V and depends on the properties of the PEDOT-PSS used and the method of its processing. and fill factor (FF). for bulk heterojunction cells. The best results were obtained for poly(3-hexylthiophene) as the matrix at a CdSe : P3HT ratio of about 10 : 90% (w/w) [67]. mA/cm2 14 12 10 8 6 4 2 I. the power conversion efficiency in organic photovoltaic cells is determined by three main parameters: the open circuit voltage (Voc). nm Fig. The power conversion efficiencies in hybrid cells depend very strongly on the shape of nanoparticles. 3 Nos.5 0 U.0 1. The highest Voc values were found for PCBM. Open Circuit Voltage Voc The maximal achievable Voc in organic cells (Voc(max)) is determined by the energy difference between the highest occupied molecular orbital (HOMO) of the donor material and the lowest unoccupied molecular orbital (LUMO) of the acceptor material (Fig. It is very likely that methods of ordering nanoparticles in the polymer matrix will be developed in the near future. For the pair of ITO/PEDOT-PSS and Al electrodes. η = 2.5 0. Such cells are referred to as hybrid since they are based on organic and inorganic semiconductors. In addition to fullerene compounds. An analogous dependence was recently demonstrated for a series of PCBM derivatives modified at the Vol.250 Isc(IQE = 1).0–2. 0.. 5–6 2008 NANOTECHNOLOGIES IN RUSSIA .0 –0. It turned out that the experimental Voc value is a linear function of the first reduction potential of the fullerene used. It is worth noting that the lowest reduction potential of PCBM corresponds to its smallest electron affinity and highest LUMO energy. The best result to date was obtained for the CdSe–P3HT system. introduced into the polymer matrix are used in organic solar cells as acceptor materials [66].g. 14) [68].01 1E-3 1E-4 1E-5 1E-6 Light 1E-7 Dark 1E-8 1E-9 1. short circuit current (Isc). A TROSHIN et al.1 0. e.9%. The experimentally observed Voc is always somewhat smaller than the theoretical maximum. and many other factors.1 0. (2) At the same time. the Voc magnitude cannot exceed the difference between the work functions of the anode and cathode (Φ1 – Φ2). which is close to the efficiency of the PCBM/P3HT system. 11. which has the lowest reduction potential among the studied materials. This dependence was first observed for a series of fullerene compounds used as acceptor materials in photovoltaic cells in combination with the donor polymer MDMO-PPV (Fig. V 0.01 1E-3 1E-4 1E-5 1E-6 1E-7 1E-8 1E-9 –1. PARAMETERS DETERMINING THE EFFICIENCY OF PHOTOVOLTAIC CELLS AND POSSIBLE WAYS TO IMPROVE THEM As mentioned above.5 0 50 100 150 200 250 300 350 Active layer thickness.

55 0.5 (110 mW) 10.0 [44] [41] [26] [42] [43] [24] [33] [34] [26] [25] [35] [36] [27] [37] [28] [38] [39] [40] [32] I * .54 0. With the use of these values and the scheme in Fig. Voc is a linear function of the first oxidation potential of the polymer (which determines the HOMO energy) [70].8 V.1 to –5. The experimental Voc values for PCBM/P3HT cells vary from 0.8 3.6660 0.1 (100 mW) 10.7 (100 mW) 4. 16) studied in photovoltaic cells in combination with PCBM.4 4. However. the use of new compounds did not lead to an increase in the total power conversion efficiency in the cells due to a decrease in the short circuit current and fill factor. Actual measurement conditions (light power) are in parentheses. the polymer causes light absorption. which is consistent with the theoretical values (with allowance for electrode losses).9 5.366 (100 mW) 6.5 (100 mW) 11.6 (80 mW) 5. An important result of this study is that higher open circuit voltages are achieved in the cells with modified PCBMs—up to 925 mV as opposed to 870 mV obtained for the control PCBM compound.61 0.1 eV for the HOMO of P3HT and –4.47 0.44 0.59 3.01 4. However.51 0.20 4.47 0.61 0.60 0. 70.0 (100 mW) ≤11.68 0.0 (80 mW) 7.996 (100 mW) 11. As expected.9 (80 mW) 12.65** 3.8 615 600 590 630 640 660 820 800 770 650–700 650–700 1040 874. the LUMO energy of the poly2008 .46 1 MDMO-PPV–4 [60]PCBM 1 MDMO–PPV–5 [70]PCBM [60]PCBM–PCPDTBT [70]PCBM–PCPDTBT [60]PCBM–PFDTBT [60]PCBM–MEH–PPV [60]PCBM–APFO3 [60]PCBM–APFO–GREEN5 [60]PCBM–PF10TBT [60]PCBM–PPE–PPV 142 10.600 0. mA/cm2 sc Voc .9 (100 mW) 9.6 (80 mW) 14.3 (100 mW) 550 560 630 602.9 4. 3 Nos. 71].3 (100 mW) 8.8 2.3 eV for the LUMO of PCBM [70].ORGANIC SOLAR CELLS Table 1.8 Ratio 1 : 0.630 0.2 1. Figure 17 shows the HOMO and LUMO energies for P3HT and PCBM.49 0.9 (80 mW) 13. the best materials to date for NANOTECHNOLOGIES IN RUSSIA Vol.2 2.9 1010 610 999 810 0. the current density was recalculated to the standard light power density 100 mW/cm2. Unfortunately.7 ≤3. Therefore.6 (100 mW) ≤9.0 ≤2. A correlation between open circuit voltages in solar cells and oxidation potentials of the corresponding donor materials was demonstrated for 26 polyconjugated polymers (Fig. 5–6 organic photovoltaic cells. phenyl group (their general formula is given in Fig.7 (100 mW) 4.66 2.46 0.5** 2.2 (100 mW) 7.7 4.8 Ratio 1 : 0.1 3.59 to 0.4346 0. The most reliable values are presumably –5. Different combinations of materials in bulk heterojunction cells System P3HT–[60]PCBM Ratio 1 : 2 Ratio 1 : 2 Ratio 1 : 1 Ratio 1 : 1 Ratio 1 : 1 Ratio 1 : 1 Ratio 1 : 1 Ratio 1 : 0.1 2. ** Values have been corrected for sunlight simulator error. % 251 Reference * In all cases.16 2.5 (100 mW) 9. the maximal Voc value for the PCBM/P3HT system is calculated as ~0.0 (100 mW) 4.66 V. 17.5 3. 15b) [69].9 eV) makes it possible to increase the open circuit voltage.58 0.250 (80 mW) 5. to decrease the HOMO level from –5.71 0. mV FF η.4 3.47 0.44 0. The use of another polymer with a lower HOMO energy (for example. the values of the LUMO energy of PCBM and the HOMO energy of the P3HT polymer from different sources vary within wide limits [61.

⎞ * ⎠n * ⎛ -⎝ PF10TBT S S N N S -.⎞ * ⎠n MEH-PPV APFO-3 O * ⎛ -⎝ O O O O -.⎞ * ⎠n PFDTBT O O N * S S PCPDTBT S N * n N * ⎛ -⎝ S N -. 3 Nos. NANOTECHNOLOGIES IN RUSSIA Vol.252 TROSHIN et al. 5–6 2008 . Molecular formulas of some polymers that provide acceptable efficiencies in solar cells with PCBM.⎞ * ⎠n O PPE-PPV 142 Fig. S N N * ⎛ -⎝ S S -. 12.⎞ S ⎠n * S APFO-GREEN5 O * * O n S N N * ⎛ -⎝ S S -.

Table 2. mV sc FF η.09 [45] [60]PCBM NANOTECHNOLOGIES IN RUSSIA PDOBTF Vol.0 500 0. % Reference Acceptor O S 0.1 S S C8H18 C8H18 PTVF ORGANIC SOLAR CELLS Nos.29 [46] O S O O O [60]PCBM 253 . mA/cm2 Voc .58 1. 5–6 [60]PCBM 2008 N * S n N S * 1.77 C8H18 n C8H18 340 0. 3 O * S S n C8H18 C8H18 * 3. Efficiencies of photovoltaic cells based on different donor polymers Donor I * .28 0.57 0.3** 390 0.

5** 560 0. mA/cm2 sc Voc . % Reference Acceptor O O O O 3.48 * 620 0. mV FF η.96 [47] [60]PCBM N N * O O O 0.4 0. 3 Nos.28 0.254 Table 2.) Donor I * .0 780 0.1 [60]PCBM N * S n N S * S TROSHIN et al.7–3. (Contd.58 1.9–0. 5–6 [60]PCBM 2008 * S n .1 [48] S S S n NANOTECHNOLOGIES IN RUSSIA * Vol. O O 2.37–0.

mA/cm2 Voc . mV FF η.Table 2.0 [49–50] [60]PCBM Vol. % Reference NANOTECHNOLOGIES IN RUSSIA N S R S S N C12H25 n N N R 3. 5–6 2008 O S * NC O n CN S 1.98 [51] C60 255 .) Acceptor Donor * I sc .49 0. (Contd.37 ~1.0 720 S N 0.18 850–860 0. 3 ORGANIC SOLAR CELLS Nos.55–0.36–0.32–3.

99 640 0.94–1. 3 MEH–PPV PBu3 Pt PBu3 S n Nos.92–2. % Reference Acceptor CN S * O NC 2. mA/cm2 sc Voc .33 0. (Contd.38–0.49–0.40 0. O 1.52 Vol. 5–6 * [60]PCBM * 0.43 0.09 810–930 S O C60 0.52–3. mV FF η.31–0.256 Table 2.09 * * O n NANOTECHNOLOGIES IN RUSSIA C60 740–780 0.) Donor I * .02 TROSHIN et al.27 [52] 2008 .

39 0.3 [54] NO2 ORGANIC SOLAR CELLS Nos. unless otherwise specified.76 540 Vol. mV FF η. mA/cm2 sc Voc .09 [55] C6H13 O * S n C6H13 O * 1.05 290 0. % Reference Acceptor F3C S N S 3.38 0.32 0. 5–6 C8H17 C8H17 S S N N n 2008 [60]PCBM S 1. 257 .5 illumination at 75 mW/cm2.) Donor I * .11 [56] [60]PCBM * In all cases.35 0.0 220 0.5 580 S N n CF3 N 0.7 [53] N NANOTECHNOLOGIES IN RUSSIA N N 1. 3 0. (Contd. the current density was measured at 100 mW/cm2. ** Current density was measured under AM1.Table 2.

56 0.04 [58] ThCBM R O O O O MEH-PPV [59] R R=Me R=n-Bu R=n-C8H17 R=CH2CH2OCH3 R=CH2CH2Ph 0. 5–6 2008 NANOTECHNOLOGIES IN RUSSIA .10 Nos.38 0.62 1.614 3.29 1.40 Vol. mA/cm2 sc Voc . Efficiencies of solar cells based on different fullerene derivatives and polyconjugated polymers Acceptor Donor I * .28 0.04 1.2 530 0.23 0.32 0.67 1. 3 0.37 2.7 [57] S O O P3HT 8.66 750 800 800 750 800 0.69 2.29 0. % Reference O O O P3HT 5.4 590 0.258 TROSHIN et al. Table 3.17 3. mV FF η.

% 259 Reference O O O O O O O O P3HT 0.18 0.27 0.98 500 0. mV FF η.83 580 0.48 O O N H2C H P3HT 0. mA/cm2 sc Voc .20 0. 5–6 2008 .62 710 0.) Acceptor O Donor I * .ORGANIC SOLAR CELLS Table 3. 3 Nos.37 [60] O CH3 O O O O N H2C H P3HT 0. (Contd.56 NANOTECHNOLOGIES IN RUSSIA Vol.

3 Nos. 5–6 2008 . Acceptor Donor * I sc .) TROSHIN et al. % Reference C12H25 O O C12H25 C6H13 * S n P3HT * 4.2 320 0. mA/cm2 Voc .02 [63] N Zn N N Bu-t NANOTECHNOLOGIES IN RUSSIA Vol.58 2. mV FF η.1 [61] P3HT Oct N N Oct Oct Oct N N P3HT 1. (Contd.260 Table 3.7 80 mW/cm2 650 0.17 0.2 650 0.26 0.13 [62] Bu-t N CH3 N N N N N Bu-t 0.

Short Circuit Current Isc The generated photocurrent density in organic solar cells depends primarily on the absorption spectrum of the active layer. Another way can be to increase the LUMO level of the fullerene compound. In addition. 5–6 into account that modified fullerene compounds should have suitable electron transport properties. it should be taken NANOTECHNOLOGIES IN RUSSIA Vol. the LUMO energy of fullerene compounds can be increased from –4. (Contd. other cell parameters (including power conversion efficiency) were not reported.01 [65] O O * In all cases.04 [64] C60 – O O CH3 N O (CH2)5 N N (CH2)5CH3 0. ∆EDg will increase. a simultaneous decrease in the HOMO and LUMO energies of the polymer is a challenging task.) Acceptor Donor I* . mer should also be decreased. 3 Nos.3 to –3. Solar cells based on P3HT show a much higher efficiency than MDMO-PPV cells due to 2008 . Voc . Only one attempt to synthesize fullerene compounds with a higher LUMO energy as compared to PCBM has been reported [69]. otherwise. however. % 261 Reference CH3 N N+ O O O – ClO4 N 1.ORGANIC SOLAR CELLS Table 3.0038 3 670 ?** 0. Such changes should lead to a nearly twofold increase in Voc in the cells [71]. From the standpoint of structural design.0 eV without loss in electron transfer efficiency. such a strong change in the electronic properties of fullerene compounds is a very complicated chemical problem.2 330 ?** 0. However. Testing these compounds in photovoltaic cells showed a certain increase in Voc. which presumably suggests that they are unsatisfactory. which will considerably decrease the light absorption range and will lead to a sharp decrease in the generated photocurrent density. sc mA/cm2 mV FF η. the current density was measured at 100 mW/cm2. Potentially. ** No separate parameters of photovoltaic cells were reported. unless otherwise specified.

60 1 E Red. As is seen in Fig. Theoretical works dealing with how the electronic properties of donor polymers affect the characteristics of organic solar cells predict that power conversion efficiencies above 10% can be achieved [70]. V –0.6 eV.95 N O N O C60 Azafulleroid Ketolactam 6 –0. 3 Nos. and the team of Prof. 18) [6]. Heeger.70 –0.262 Vacuum TROSHIN et al. respectively. the light absorption parameters of the donor and acceptor materials are determined by ∆EDg and ∆EAg.70 0.65 0. 17. The difference in 100 nm causes a twofold increase in current density in going from MDMO-PPV cells to cells based on P3HT. who reported in mid-2007 a power conversion efficiency of about 5. NANOTECHNOLOGIES IN RUSSIA Vol. Inc. Therefore.80 0. An alternative way to increase the density of the photocurrent generated in photovoltaic cells is using accep- Voltage. Linear dependence of Voc on the reduction potential of fullerene compounds (n-type materials in the cells) (taken from [68]).75 0.5% achieved in cells based on a donor polymer with a broad absorption spectrum [31].0 eV and their use in photovoltaic devices. the difference in the absorption spectra of these donor materials.55 –0. Φ1 LUMO e– LUMO Φ2 E = hν Voc(max) HOMO Donor HOMO Acceptor – + Fig. This is due to the fact that the intensity of sunlight is maximal in the range 570–670 nm (Fig. respectively.2–1. V 0. 14.65 Azafulleroid 5 (a) (b) O O S1 = 0. the absorption spectrum of at least one of the materials used should be extended. No information on solar cells based on polymers with precisely such properties is currently available. 13. A. the donor material determines the spectral range of light conversion. in almost all known systems with fullerenes where ∆EDg < ∆EAg.85 PCBM 0. Progress has been achieved only by Konarka Technologies. Studies are being performed worldwide on the creation of donor polymers with ∆EDg less than 2. 5–6 2008 . which in 2006 certified cells with an efficiency of 5% based on an unknown polymer [72]. whereas P3HT absorbs up to 670 nm [6–8]. Variable parameters are the HOMO energy of the polymer and the bandgap (the energy difference between the HOMO and LUMO of the polymer). Figure 19 shows a diagram that can be referred to as the solar cell efficiency map for cells based on PCBM and different polymers. To further increase the generated photocurrent density. which are plotted as ordinates and abscissas.9 eV and a bandgap of 1. MDMO-PPV absorbs light only up to 570 nm. The curves in the diagram show the change in the maximal efficiency of organic solar cells as a function of these properties of the polymers.60 0..55 O O Ketolactam PCBM C60 Fig. It follows from the diagram that an optimal polymer should have a HOMO energy above 3. Open circuit voltage in photovoltaic cells.

800 4. The attachment of organic groups to fullerene significantly impairs electron transport properties. but charge transport is hindered due to the lack or strong fragmentation HOMO position. The mobility of charge carriers in the best polyconjugated polymers is usually 10–3–10–1 cm2/(V s) and is sometimes close to 1 cm2/(V s) [73]. However.08 –1.13 –1. The optimal donor–acceptor phase separation is important for ensuring not only charge transport to electrodes but also efficient generation of charges at the phase interface [8]. the hole transport properties of polyconjugated polymers are quite satisfactory. 4- O M y- 900 ePC BM M Rn O O CH3 ePC BM ePC BM M O 6- 750 –1. Fill Factor The fill factor in photovoltaic cells is determined by many parameters. The transport properties of fullerene compounds depend strongly on the structure of the organic addends attached to the fullerene cage. 3 Nos. mV 800 600 600 400 200 0 –200 0 400 200 0 200 400 600 800 1000 1200 Onset of oxidation.2-dichlorobenzene (taken from [69]). the mobility of electrons in PCBM films is 10–2–10–3 cm2/(V s).6 –4. 15. Therefore.10 –1. 3. it is believed that the optimal size of fullerene and polymer domains should be close to the diffusion length (free path) of excitons in a given material.11 –1. such attempts have been unsuccessful thus far.ORGANIC SOLAR CELLS (a) ePC e. 4- O M 3. this value is 5–15 nm for both PCBM and a polyconjugated polymer and can vary significantly as a function of the purity of materials and film production conditions [6–8]. The charge-carrier mobility in composite PCBM/polymer films depends strongly on both the ratio of the components and the morphology (microstructure) of a film. mV O 3.4 –5. red (Vvs. Results are given for cells in which the active layer was deposited from (squares) chlorobenzene and (circles) 1. For example. This is due to the fact that organic addends are insulators and prevent electron transport over the fullerene π systems.8 –5. By rough estimate. 5–6 2. The addition of bulkier groups to the fullerene cage decreases the mobility of electrons at least by one to two orders of magnitude [61. 70]. Fc/Fc+) Fig.8 1200 1000 Measured Voc. (a) Open circuit voltage Voc as a function of the reduction potential of metanofullerene derivatives PCBM with methoxy substituents in the phenyl ring (b).0 –5. Linear dependence of Voc on the oxidation potential of polyconjugated polymers (p-type materials in the cells) (taken from [68]). tor materials that absorb in a broad spectral range. Morphology is taken to mean the formation of separate phases of the donor and acceptor components in films. The transport properties of materials are the most important among them. mV 1200 800 Fig. eV –4.12 –1. MORPHOLOGY OF THE PHOTOACTIVE LAYER OF CELLS It has been reliably established that both the shortcircuit current density (Isc) generated by a photovoltaic cell and the fill factor (FF) depend very strongly on the microstructure or morphology of the photoactive layer of the cell. 1.2 –5. If the sizes of domains of separate phases are considerably smaller than the above value.6 –5. Nonmodified fullerene C60 is the best among the known organic n-type semiconductors: the electron mobility in C60 films is as large as 8 cm2/(V s) [73]. As a rule.BM PC BM 263 (b) Voc. 5- 2- O 2.09 –1. Figure 3 schematically shows that the phases of the donor and acceptor materials in bulk heterojunction cells should be orderly arranged for the conduction channels for both types of charge carriers to appear. 16. 4- 850 4- M phases. ePC BM PC BM M O M PC BM et hy le ne dl ox 2. 2008 . as well as mutual ordering of these NANOTECHNOLOGIES IN RUSSIA Vol.07 E1/2. the charge separation efficiency is retained (and can even be improved).

A striking example is a twofold increase in current density in MDMO-PPV/PCBM cells caused by the use of another solvent for film application [22]. LUMO of a new fullerene compound ∆E g D P3HT –3. 105cm–1 4 × 1018 AM 1.0 MDMO-PPV P3HT PCBM 5 × 1018 Absorption coefficient.0 LUMO TROSHIN et al. of conduction channels.8.264 –2. 5–6 2008 NANOTECHNOLOGIES IN RUSSIA .5) conditions (taken from [4]). respectively [22]. if phase domains are more than 100–500 nm in size..5 photon flux.. chlorobenzene gives much better results.5 0 300 Silicon band edge 2 × 1018 1 × 1018 400 500 600 700 800 900 Wavelength λ. The influence of the morphology of photoactive films on the efficiency of organic photovoltaic cells is often underestimated. Such a strong effect of the solvent on the efficiency of photovoltaic cells is due to the morphology of photoactive films..0 2. nm 1000 1100 0 1200 Fig.3 LUMO Voc(max) ∆E g A –4. Figures 20b and 20c show the photomicrographs (atomic force microscopy data) of films deposited from chlorobenzene and toluene. As is seen.5 1.. Figure 20a shows the current–voltage curves of solar cells manufactured with the use of toluene and chlorobenzene as solvents: as is seen.1 HOMO Fig. 3. 17. P3HT. Conversely. the film deposited from toluene is rather inhomoVol. It is important that the optical characteristics of the films are nearly independent of the solvent used..0.–6.0 0.1 HOMO PCBM HOMO of a new polymer –6.5 2..7. and fullerene compound PCBM and the solar spectrum under AM1. 3 Nos. 18..7. this adversely affects photoinduced charge separation.5 (Air Mass 1. Scheme of the frontier orbitals of the P3HT/PCBM system. Only recently has it been clearly demonstrated that morphology is a crucial parameter that determines the operation of a photovoltaic cell. Absorption spectra of the polymers MDMO-PPV. The donor– acceptor contact area sharply decreases with an increase in the degree of phase separation.–5. m–2s–1nm–1 3 × 1018 1. The way to increase Voc by reducing the HOMO energy of the polymer and increasing the LUMO energy of the fullerene compound.. The excitons generated in large domains of donor and acceptor materials are not able to reach the boundary and are lost inside the domains without making a contribution to charge generation.–4.–3.

2 HOMO –4.00 4.2 2. The film deposited from chlorobenzene is considerably more homogeneous: the size of PCBM nanoclusters does not exceed 15 nm. However.0 eV PCBM Fig.00 1. The power conversion efficiency increases from 1. 21) and sharply improves the cell characteristics [27].0 8. which decreases the efficiency of photoinduced charge separation.00 HOMO Donor HOMO–6.00 2.0 to 10.00 –3.00 8.00 6.0 3. eV 7.4 0.7 eV –3. geneous.00 –3.8 0.2 0.00 9.ORGANIC SOLAR CELLS –4.1 1.0 2.7 2.00 10.6 0.00 5. V 1 µm 2 Chlorobenzene-cast active layer 1 1 0 0 1 µm 2 0 Fig. Current density. As is seen.3 0.8 D E g .1 to 3.00 HOMO –5. 19.8%. eV 1.00 265 10.00 –3. 3 Nos.00 6.00 2. Figure 22 shows the experimental current–voltage curves obtained by us for solar cells with the PCBM/P3HT active layer. Therefore. There are bright areas 100–250 nm in size. the open circuit voltage changes from 550 to 610 mV. 5–6 films from solution under ordinary conditions leads to unsatisfactory characteristics of photovoltaic cells.6 5. Photomicrographs of the films deposited from (b) chlorobenzene and (c) toluene (taken from [21]). 20. The PCBM–polymer interface is very small.5 1. heat treatment of the active layer at 150°C for 10 min considerably improves all parameters of a photovoltaic device. which correspond to PCBM nanoclusters.00 3.7 0.8 HOMO energy.4 2.4 4. The short circuit current increases from 5.9 0 Voltage. and the fill factor increases from 38 to 59%. Diagram illustrating the dependence of the maximal efficiency of photovoltaic cells on the HOMO energy and bandgap EDg of the polyconjugated polymer (taken from [70]).00 9.00 11.9 mA/cm2.1 0.8 eV D 0 1. 2008 .00 LUMO Eg 3. careful optimization of morphology is necessary for the best characteristics of photovoltaic cells to be achieved.3 eV –3.5 0. mA/cm2 0 (a) –1 Toluene-cast active layer (b) 10 (c) 100 50 0 nm 2 5 0 nm 2 –2 –3 –4 –5 –6 0 0.00 7.00 ∆E LUMO–4. Deposition of P3HT/PCBM NANOTECHNOLOGIES IN RUSSIA Vol. (a) Current–voltage curves of the cells made with the use of toluene and chlorobenzene. heating the films to 120–150°C results in ordering of the donor and acceptor phases (Fig. Control over morphology is also important for the P3HT/PCBM system [24]. Most PCBM clusters in the film deposited from toluene are isolated.

5 1. V Fig. (a) (b) (c) 100 nm Fig. these currents should be equal) and the open circuit voltage is equal to the sum of the voltages of the constituent cells.266 TROSHIN et al. Current balance requires careful optimization of the thickness of each photoactive layer. At the output of the tandem cell. There are some examples of tandem solar cells described in the literature [75–80]. 23).0 Voltage. Primarily. HR TEM images of P3HT/PCBM films (left) without heating and (center) after heat treatment at 150°C for 30 min and (right) 1 h. 5–6 2008 NANOTECHNOLOGIES IN RUSSIA . a tandem of two photocells based on thin semitransparent films gives. 3 Nos. does not lead to better results because of low charge mobilities (charge transport to electrodes is hampered). Change in the current–voltage curves of the PCBM/P3HT photovoltaic cell after heat treatment at 150°C for 10 min. 22. these are cells in which the upper and lower cells are identical and consist of the same materials. as a rule. TANDEM ORGANIC SOLAR CELLS Tandem photovoltaic cells are those in which there are two or more cells sitting atop one another (arranged in stacks).5 0 0. which leads to a sharp decrease in the efficiency of the tandem cell as a whole. 21. the short circuit current is equal to the minimal current among the those of the constituent cells (optimally. notwithstanding 100% light absorption. A major disadvantage of tandem cells is the need to equate the photocurrents generated in each of the cells in order to achieve the highest efficiency. much better results than a sepVol. Current. The photoactive layers in organic solar cells are always relatively thin films (the overall thickness is no more than 50–100 nm) that absorb only 40–60% of incident light.0 –0. Therefore. It is worth noting that a change in the incident light intensity or angle disturbs the balance between the photocurrents generated in the upper and lower cells (the cells give different photocurrent densities). The use of thick films. mA/cm2 10 Before heating After heating 5 0 –5 –10 –1. which are formally connected in series since they have a shared electrode that functions as the cathode for one cell and the anode for the other (Fig.

Molecular formulas of some polymers used in tandem cells.5 2. Acm–2 V 10–2 Al 10–3 C60 ZnPc:C60 15 nm 30 nm 10 nm 10 nm ≈ 150 nm 10–4 ZnPc C60 PCBM P3HT 10–5 –2. Tandem cells that convert light in a wide spectral range are the most promising. the upper cell converts light in the longwavelength range. N * S S S N S N n * PCPDTBT N S S n O O O O N * S S N S n PFDTBT PTBEHT Fig.0 PEDOT:PSS ITO Glass –1. In such cells.0 Fig. (a) Scheme of layers in a tandem photovoltaic cell. (b) Current–voltage curves for single PCBM/P3HT and C60/ZnPc cells (solid lines) and for the tandem cell ITO/PEDOT:PSS/P3HT:PCBM/C60/Au(1 nm)//ZnPc/C60 + ZnPc/C60/Cr/Al (taken from [77]).0 1.5 –1. 77]. 3 Nos. arate photovoltaic cell with the optimal thickness of the photoactive layer [75. 24. conversely. 23.5 0 Voltage. V 0.45 267 Al cathode Active layer II Shared electrode Active layer I PEDOT:PSS ITO anode Glass 10–1 Current.8 mAcm–2 Voc = 1020 mV FF = 0. the lower cell usually converts light in the short-wavelength NANOTECHNOLOGIES IN RUSSIA Vol. 5–6 range and is transparent in the long-wavelength range.ORGANIC SOLAR CELLS P3HT:PCBM Tandem ZnPc:C60 Isc = 4.5 1. One of the most attractive solutions is the combination of P3HT with PCBM in the lower cell (a bulk heterojunction cell) and of ZnPc with C60 in 2008 .0 –0.

Characteristics of some tandem organic solar cells Structure of layers in the cell Single: ITO/PEDOT:PSS/MDMO–PPV:PCBM/Al Tandem: ITO/PEDOT:PSS/MDMO–PPV:PCBM/ITO(20 nm)/PEDOT: PSS/MDMO–PPV:PCBM/Al Single: ITO/MeOTPD/C60 + ZnPc/C60/Al Tandem: ITO/MeOTPD/C60 + ZnPc/C60/Au/MeOTPD/C60 + ZnPc/C60 Single: ITO/PEDOT:PSS/P3HT:PCBM/Al Single: ITO/PEDOT:PSS/ZnPc/C60 + ZnPc/C60/Cr/Al Tandem: ITO/PEDOT:PSS/P3HT:PCBM/C60/Au(1 nm)//ZnPc/C60 + ZnPc/C60/Cr/Al Single: Cr/Au/PEDOT:PSS/PFDTBT:PCBM/LiF/Al** Single: Cr/Au/PEDOT:PSS/PTBEHT:PCBM/LiF/Al** Tandem: Cr/Au/PEDOT:PSS/PFDTBT:PCBM/LiF/Au/PTBEHT:PCBM/LiF/Al* Single: ITO/PEDOT:PSS/P3HT:[70]PCBM/Al Single: ITO/PEDOT:PSS/PCPDTBT:[60]PCBM/Al* Tandem: ITO/PEDOT:PSS/PCPDTBT:[60]PCBM/TiOx /PEDOT:PSS/P3HT: [70]PCBM/Al** Tandem: ITO/CuPc/CuPc + C60/C60/PTCBI/Ag/mMTDATA/CuPc/CuPc + C60/C60/BCP/Ag*** I * .2 2.59 0. ** The molecular formulas of the polymers PFDTBT. 3 Nos.57 4. The composition of layers and characteristics of available tandem cells are compiled in Table 4. Inc.7 1030 0.2 10.7% have been reported [80]. In addition. Table 4. a power conversion efficiency of about 5.10-phenanthroline).8 1 0. mA/cm2 Voc .5 Reference [75] [76] [77] [78] [79] 9.9 0. organic photovoltaics has evolved from a pure science to a high-priority field of worldwide importance. The first success was achieved by Konarka Technologies. power conversion efficiencies of about 6. 23. In our opinion. which in 2006 certified the first cell with an efficiency of 5%.59 0. and PCPDTBT are shown in Fig.45 0.8 840 1340 500 990 550 470 1020 900 500 1400 630 660 1240 FF 0.6%.67 η.3 4.55 0. *** The molecular formula of PTCBI is shown in Fig. Therefore.59 5. Table 4 shows that.35 0. The model system based on composites of fullerene compounds and substituted poly(p-phenylenevinylene)s had exhausted itself in providing a power conversion efficiency of 2. There are no doubts that the coming boom in new polymer materials will set new records for efficiency. in particular.6 4. The next step was to use poly(3hexylthiophene) as the donor polymer.7–6.8 2.1 2. PTBEHT. efficiencies as large as 5.55 0.56 0.8 8. efficient tandem solar cells have been reported in which the upper and lower cells contain blends of fullerene derivatives ([60]PCBM and [70] PCBM) with polyconjugated polymers [79].6 0.7 3.9-dimethyl-4. Vol.9 10. m-MTDATA is the hole conductor 4.7 [80] * In all cases. 5–6 2008 NANOTECHNOLOGIES IN RUSSIA . many researchers doubt such record efficiencies.5 9. In mid-2007.1 3.50 0. 5.5% are being extensively developed.7-diphenyl-1.50 0. These results have neither been reproduced by other researchers nor confirmed by independent experts at the photovoltaic cell standardization center.4''-tris[3-methylphenyl(phenylamino)amino]triphenylamine.0 6.64 0.8 9.50 0.0%. which is the theoretical maximum for this system.1 15. which in combination with polyconjugated polymers gives rather high power conversion efficiencies.2 7. BCP is the electron transport layer bathocuproine (2.4. power conversion efficiencies of about 6% are undoubtedly encouraging since they unambiguously demonstrate the considerable potential of organic photovoltaics.3 3. % 2.5% have been achieved [79].23 0. Tandem organic solar cells providing power conversion efficiencies of about 5. 24.37 0. the upper cell (a bilayer cell) [77].5% was reported for cells based on new lowbandgap polyconjugated polymers. the current density was measured at 100 mW/cm2. A key role in this breakthrough has been played by fullerene-containing materials. It is currently understood that further improvement in the efficiency of solar cells requires other polyconjugated polymers with special properties. mV sc 4. for the cells based on low-molecularweight materials. those having strong absorption bands in the near-IR region.268 TROSHIN et al. CONCLUSIONS In the past decade..45 0.6 2. and the structural formulas of some materials used in tandem cells are shown in Fig. which made it possible to increase the efficiency to 4. for the tandem cells based on polyconjugated polymers and fullerene compounds.

Troshin.. “Self-Organized Discotic Liquid Crystals for High-Efficiency Organic Photovoltaics. 121 (2007). 15. “Efficiency Enhancement in Low-Bandgap Polymer Solar Cells by Processing with Alkane Dithiols. 20.. Yang. 435–441 (2004). 90 (14).” http:// www. 18. et al. Sariciftci. Funct. Müllen. Shaheen. B. Sariciftci.” J. S. S.513. Carbon Nanostruct. B. Y. Kozlovski. J.” Adv. I. S. C. “OrganicBased Photovoltaics: Toward Low-Cost Power Generation. Sariciftci. Sariciftci. Rand. S. 2008 . et al. A. Phys. K. et al. Phys. Funct. P. Mater. A. 15. E. 40–42 (2007). Phys. Boiko. “Enhanced Open-Circuit Voltage in Subphthalocyanine/C60 Organic Photovoltaic Cells.. 26.. M.” Adv.5% Efficient Organic Plastic Solar Cells” Appl. Polym. R. Kim.3206). Männig.. R.) 18. Xue. 33–36 (2005). Brabec. Y. C. Jabbour. 16. 31..atip. Peumans and S. J. Koeppe.030: “The Solar Cell Industry in Japan. 28. Asian Technology Information Program (ATIP): Report ATIP97. Koeppe. 201 120 (2005). 503–507 (2004). Sci. “Thermally Stable.” Appl. 22. 19. Reyes-Reyes. Janssen. F. C. J. G.030r. Phys. J.” Fullerenes. P. 3 Nos. Chem. R. H. A.” Angew. Ambacher. Mater. G. S. S. Uhrich.11. et al.” Adv. 233 508 (2005). Shrotriya.” Chem. 16. and C. S.” MRS Bull. 5749–5752 (2005). K. C. 8. Am. Mater. Funct.” Org. 12. S. and N. Forrrest. H. 7. et al. Troyanov. Nanotubes. Chem. 244 102 (2005). Mater. Wienk. C. D.. 5–6 19.11. Peet. R. P. 5363– 5372 (2007). H. K. H.html 2. (Weinheim. M. M. K. J. et al. J. S. 10 (2005). D. C. S. 27.” Chem. 18.97/atip97. C. 17. L. Lett. D. 8108– 8109 (2006). et al. 42. 9.” Adv.solarbuzz. 17.” MRS Bull.htm 3. 1924–1945 (2004). 48 (2). “Material and Device Concepts for Organic Photovoltaic: Towards Competitive Efficiencies. et al. M. A. M. Alévêque. “MesoStructure Formation for Enhanced Organic Photovoltaic Cells. J. and G. 29. W. R. E. P. S. E. Hoppe. “Efficient Vacuum-Deposited Organic Solar Cells Based on a New Low-Bandgap Oligothiophene and Fullerene C60. 30. I. Soc. 12. et al. Mater. 13.” Adv. and 02. Yao. Waldauf. Schilinsky. 7. Kroon. F. 16.. Efficient Polymer Solar Cells with Nanoscale Control of the Interpenetrating Network Morphology. 45–61 (2006). S.org/ATIP/public/atip. 1617–1622 (2005). and N.3358. “Efficient [2 + 3]-Cycloaddition Approach to Synthesis of Pyridinyl Based [60]-Fullerene Ligands. Forrest. 87 (23). Verhees. W. P. 10. Res. T. 13. C.” Appl. Coakley and M.. S. 32. Bearing Chelating Pyridyl Groups and Zinc Phthalocyanine for Organic Solar Cells. Funct.11. M. Waldauf. S. Phys. “Accurate Measurement and Characterization of Organic Solar Cells.. 15–26 (2001)..reports. 79. Brabec. 24. (Weinheim.. B. Lyubovskaya. N. Lett. and J. Morana. 86 (20). 21. 34. “Complexation of Pyrrolidinofullerenes and Zinc-Phthalocyanine in a Bilayer Organic Solar Cell Structure. Drechsel. Lett. REFERENCES 1. http://www. 4533–4542 (2004). Muhlbacher. “Organic Solar Cells: An Overview.. Kroon. 126–128 (2001). Li. 5. Schulze. Ma. Al-Ibrahim. 33. X. 841–843 (2001). 2016–2023 (2006). Hoppe and N. 1669–1672 (2006). Mater. “Light-Emitting Organic Solar Cells Based on a 3D Conjugated System with Internal Charge Transfer. J. Mater. Mutolo.” Thin Solid Films 451. O. J. 16. Brabec. R. Ger. Mater.” Appl. et al. Lett. Schüppel. Brabec. “Conjugated Polymer Photovoltaic Cells.” Adv. 16. S. 23. E. Rittberger. 183–185 (1986).3209. Schmidt-Mende. A. Scharber.ORGANIC SOLAR CELLS 269 ACKNOWLEDGMENTS This work was supported by the Russian Foundation for Basic Research (project no. 1119–1122 (2001). 2884–2889 (2006). “Polymer Solar Cells. Funct. Phys. “Efficient Methano[70]Fullerene/MDMO-PPV Bulk Heterojunction Photovoltaic Cells. A. “Effects of Solvent and Annealing on the Improved Performance of Solar Cells Based on Poly(3-Hexylthiophene): Fullerene. Aernouts. Cravino. J. 2872–2875 (2006).” Adv. E. L. and C. Gobsch. 12. “Determining the Internal Quantum Efficiency of Highly Efficient Polymer Solar Cells through Optical Modelling. 14. 30. Troshin. “Inverse Relation between Photocurrent and Absorption Layer Thickness in Polymer Solar Cells. Mater. Lett. N. Leriche. N. and N. P. C. D. “High Photovoltaic Performance of a Low-Bandgap Polymer. Mater. Mater. Ginley. J. P. 3033–3037 (2006). Sariciftci. and G. Sariciftci. Status Solidi RRL 1 (1). H. Lett. V. Dewald. 4.” Science (Washington) 293. Shokhovets. 87 (24). Veenstra. Cheyns. 497– 500 (2007). Hoppe and N.” Thin Solid Films 451. 128 (25). Gobsch. et al. “Organic Solar Cells with Sensitivity Extending into the Near-Infrared Region.. Kim. F. Ed. Mater.” Nat. L. Gommans. 02. N. Coates. S. H. 02. R. Hummelen.. et al. J. “2. Int. “Two-Layer Organic Photovoltaic Cell. and G. R. Rand. M. Fechtenkötter.” Appl. Shaheen. H. Peregudov.” Adv. Chem. Lett. Troshin. Padinger. 515–517 (2004).) 18. N. Hoppe and N. “Supramolecular Association of Pyrrolidinofullerenes NANOTECHNOLOGIES IN RUSSIA Vol. et al. 11.” Adv. Sariciftci. Lett.” Adv.com/StatsCosts. P. “High-Efficiency Organic Solar Cells Based on Single or Multiple PIN Structures. 3371–3375 (2003). K. Tang. 6. Schilinsky. J. 11. Ger.” Appl. Mater. 30. “ElectroOptical Study of Subphthalocyanine in a Bilayer Organic Solar Cell. 6. P.513. 85–88 (2003). Gong.” J.” Phys. et al. M. Phys. 2653–2658 (2007). J. Yang. “Very-High-Efficiency Double-Heterostructure Copper Phthalocyanine/C60 photovoltaic cells. “Polymer–Fullerene Bulk Heterojunction Solar Cells. “Plastic Solar Cells. C. McGehee. “Effects of Postproduction Treatment on Plastic Solar Cells. 07-03-01078-a) and the Federal Agency for Science and Innovation (State Contract nos. Hauch.” Appl. 25.513. et al. “Morphology of Polymer/Fullerene Bulk Heterojunction Solar Cells. Sariciftci.. “Performance Analysis of Printed Bulk Heterojunction Solar Cells. A. S.. 19. et al. 78. Funct. W.” J. Sensfuss. 143 506 (2007). Mater. Slooff. and S. O. Mayo. Hummelen. M.

et al. C. J. 3371–3375 (2003). Winder. D. “Extended Photocurrent Spectrum of a Low-Band-Gap Polymer in a Bulk Heterojunction Solar Cell. Björström. S. Ger. Muhlbacher. 3531–3546 (2006). et al. et al. F. Mater. K. et al. Mater. 17. Fernandez. J.. “Origin of the Enhanced Performance in Poly(3-Hexylthiophene) : [6. “Solar Cells Based on Poly(3-Alkyl)thiophenes and [60]Fullerene: A Comparative Study. and N. Deng. Commun. L. Kroon. Chem. 15. 1887–1889 (2006).. Demadrille. “A LowBandgap Semiconducting Polymer for Photovoltaic Devices and Infrared Emitting Diodes. A. D. Mater. Perzon. L. 12.” Adv. 37.” Adv. Funct. E. Chem.) 15. L. “Novel Regiospecific MDMO–PPV Copolymer with Improved Charge Transport for Bulk Heterojunction Solar Cells.. “Thienyl Analog of 1-(3-Methoxycarbonyl)propyl-1-Phenyl[6. “Low-Band-Gap Poly(di-2-thienylthienopyrazine) : Fullerene Solar Cells. 42. Sieval. 54. “Diphenylmethanofullerenes: New and Efficient Acceptors in Bulk-Heterojunction Solar Cells. et al. M. 15. J. F. Lee.” Appl. M. Andersson. et al. Zhang.” J. Delgado. Phys.. 2065–2070 (2002). 56. G. S. E. Phys. 43. Oswald. et al. “Sensitization of Low-Bandgap Polymer Bulk Heterojunction Solar Cells. Firon.” Adv. P. Energy Mater. M. Lett. and D. 15. Perzon.. 62. B. et al. M.. Egbe. Wienk. et al. C.” Adv. “Enhanced Photocurrent Spectral Response in Low-Gandgap Polyfluorene and C70-Derivative-Based Solar Cells. Wang. Zheng.. Mater.. et al. 14.. J. et al. Mater. H. 153 511 (2006).. Phys. 709–712 (2002). 44. Funct. “High-Efficiency Photovoltaic Devices Based on Annealed Poly(3Hexylthiophene) and 1-(3-Methoxycabonyl)-Propyl-1Phenyl-(6. Lett. F. Hoppe. X. S. 5158–5163 (2005). Phys. Roman. 40.. Tontcheva. “High Molecular Weights. 55. C. Mater. Wienk. 1665–1670 (2005). Phys. M. Commun. Leroy. X.” J.. 16. P.” J.” Adv. Chem.) 10. 403–404 (2002). Lett. 1665–1670 (2005). UK). Mammo. C. Funct. B 108.” Appl. “Plastic Solar Cells Based on Fluorenone-Containing Oligomers and Regioregular Alternate Copolymers. Geri. No. N. 15. E. Leroy. 083 506 (2005). Sariciftci. 5–6 2008 35. et al. 251–256 (2005). 3 Nos. “Efficient Methano[70]Fullerene/MDMO–PPV Bulk Heterojunction Photovoltaic Cells. R. “Stabilization of the Nanomorphology of Polymer–Fullerene "Bulk Heterojunction” Blends Using a Novel Polymerizable Fullerene Derivative. 2169–2173 (2006). Mater. Scharber. “Photovoltaic Activity of a PolyProDOT Derivative in a Bulk Heterojunction Solar Cell. Funct. M. 78. 36. N. Sanchez. 89 (21). J. 1979– 1987 (2005).6]-Methanofullerene for Bulk Heterojunction Photovoltaic Devices in Combination with Polythiophenes. Hiorns. M. et al. de Boer. L. W. M. G. N. “Light Harvesting Tetrafullerene Nanoarray for Organic Solar Cells. and K.. Pettersson. Atienza. Campos. “2. Parisi. J. 87 (8). Lett. Zhang. L. Veenstra. “Platinum-Acetylide Polymer Based Solar Cells: Involvement of the Triplet State for Energy Conversion. Perzon. “Photovoltaic Action of Conjugated Polymer/Fullerene Bulk Heterojunction Solar Cells Using Novel PPE–PPV Copolymers. 2263–2273 (2006). R.. Ed. I. X. A. M. New Low-BandGap Alternating Polyfluorene Derivatives for Photovoltaic Cells.” 489. 157–162 (2006). Sol. 841–843 (2001). 57. Vol. G. (Weinheim.” Adv.” Chem. Camaioni. Oswald. S. M. M. 41.. 17 4031–4033 (2005). M. Lett. Brabec. 15. J. Popescu.” Sol. Sariciftci. A. 42.. et al. Matt. M. et al. et al. von Hauff. Verhees. “High Quantum Efficiency Polythiophene/C60 Photodiodes. Mozer. Zhang. B. K. 514– 516 (2006). 51. E.. Denk. (Weinheim. Lett. Int. Cells 90. Campos. H. S. 59. et al. Polydispersities. Funct. et al... L. C.” Adv. S. 63. “Influence of Solvent Mixing on the Morphology and Performance of Solar Cells Based on Polyfluorene Copolymer/Fullerene Blends. C. 49.... S. N. Günes. S.” Chem..” Appl. (Cambridge.” Adv. Turbiez. et al. S. Reynolds. 50.4-Phenylene Vinylene] and C60 Dicarboxylate. Wang. and J.” Thin Solid Films 373.” Chem. 45. Schanze. Mater. M. Perzon. “High-Performance Polymer Solar Cells of an Alternating Polyfluorene Copolymer and a Fullerene Derivative. Chem. C. Funct. 52.5% Efficient Organic Plastic Solar Cells. P. Sariciftci. Zhang. 745–750 (2005). H. J. C. 58. UK). 53. et al. Mater. A. Cho. Bettingnies. A. Funct. Reyes-Reyes. Mozer. F. A. 774–777 (1998).” Appl. Kim. 39. 12. R. M. 3462–3467 (2004). Günes.” Appl. G. 16. Mater. S. Xie. (Cambridge. 667–674 (2006)." Thin Solid Films 511–512. “LowBandgap Alternating Fluorene Copolymer/Methanofullerene Heterojunctions in Efficient Near-Infrared Polymer Solar Cells. Brabec. L. W. 15. Manno. Y.. et al. K. X. A. Nummelen. and Annealing Temperatures in the Optimization of Bulk-Heterojunction Photovoltaic Cells Based on Poly(3-Hexylthiophene) or Poly(3-Butylthiophene). Shaheen. et al. S. “The Effect of Side Chains on the Performance of Solar Cells Fabricated from Poly[2-Methoxy-5-(2'-Ethylhexoxy)-1. 5081–5083 (2004). “Enhanced Photocurrent Spectral Response in Low-Bandgap Polyfluorene and C70-Derivative-Based Solar Cells. Mater. NANOTECHNOLOGIES IN RUSSIA . Jespersen. A.” Adv. W. Funct. Zhou. 60. Ger. Winder. Riedel. M. et al. 61.) 18. 5235–5242 (2004). Ger. Garlaschelli. J. L. 88 (15). 38. Struijk. Kwak.. H. Gi. F. et al. Drees. 89 (1). Mater.270 TROSHIN et al.. Mater. (Weinheim. X. et al. R. “Polymer Solar Cells Based on a Low-Bandgap Fluorine Copolymer and a Fullerene Derivative with Photocurrent Extended to 850 nm. Phys. van 't Hof. Wang. L. “Infrared Photocurrent Spectral Response from Plastic Solar Cell with Low-Band-Gap Polyfluorene and Fullerene Derivative.6)C61 Blends. E.6]-Phenyl C61-Butyric Acid Methyl Ester Solar Cells upon Slow Drying of the Active Layer. 213 507 (2006). Guo. 46.” J.” Adv. Kim.” Appl. Winder. 5. M. V. Carrolla.” Adv. Q. 48. Wang.. E. Mater. 85.” Angew. Mihailetchi. Svensson. 47. H. 988–991 (2003). Chem. No. 1547–1552 (2005). 012 107 (2006). F. Phys. L. F. R. C. C. Mater. Hoppe. M. J. D. et al. J.

“Solution-Processed Organic Tandem Solar Cells. Sakai. Phys. Brabec. 67.. et al. Res. 093 511 (2006). Mater. 073 502 (2006). et al. Lett. J. Cravino. W.” Science (Washington) 317. Gebeyehu. 700–704 (2003).. D. A.” Adv. et al. J. 3557–3560 (2006). S. Hoppe. and A. Y. F. T.. Green. 76. R. Lett. 68.” Synth. King. 118. P. “The Interplay of Efficiency and Morphology in Photovoltaic Devices Based on Interpenetrating Networks of Conjugated Polymers with Fullerenes. 65. Kooistra. C. Met. B. “Solar Cell Efficiency Tables. M. Phys. 36. 789–794 (2006). 11. Prall. Lee. B. T. et al. D. Lett. Uchida.” Appl. “Origin of the Open Circuit Voltage of Plastic Solar Cells.” 8. Meng. S. R.. U.. Singh and N. “Design Rules for Donors in Bulk-Heterojunction Solar Cells—Towards 10% Energy-Conversion Efficiency. et al. C. D... B. Lett. A. Photovoltaics 14. Padinger.) 18. K. 72.” Appl. et al. C. 16. Phys. 1–9 (2001). F. K. NANOTECHNOLOGIES IN RUSSIA Vol.ORGANIC SOLAR CELLS 64. Phys. K. 79. 374–380 (2001). Loi. C. N. Xue. Mater. M. Emery. Mater. Greenham. F. Dennler. 77. F. Hadipour. Meissner. J. Ger. Dittmer. Rev. Lett. J. 5757–5759 (2004). Drechsel. Blom. B. 979–986 (2005). J. D. “Enhanced Spectral Coverage in Tandem Organic Solar Cells. J. et al. F. Muhlbacher. 74. Koeppe. et al. 13. M. J. Kim. Kawano. Lett 85. Wildeman. Forrest. Huynh. et al. N. J. M. H. Chem. M.” Org. “Increasing the Open Circuit Voltage of Bulk-Heterojunction Solar Cells by Raising the LUMO Level of the Acceptor. Koppe.” Adv. Denk. et al. Hua. Funct. 88 (9). W. Brabec. “Ultimate Efficiency of Polymer/Fullerene Bulk Heterojunction Solar Cells... “Hybrid Nanorod–Polymer Solar Cells. 271 73. Funct.. 69. K.. “Efficient Organic Solar Cells Based on a Double p–i–n Architecture Using Doped Wide-Gap Transport Layers. 78. (Weinheim. P. Männig. Kastenberg. Kozlowski. 199– 230 (2006). L. Sariciftci. Koster. 455–461 (2006). et al.” Science (Washington) 295. and P.” Appl. “Asymmetric Tandem Organic Photovoltaic Cells with Hybrid Planar-Mixed Molecular Heterojunctions. Mihailetchi. 15.” Annu. “Counterion Effects in Cyanine Heterojunction Photovoltaic Devices. Nishimori. 88 (7). Knol.” Adv. E. 073 514 (2006). 244 102 (2005). 5–6 2008 . Chem. Chem. A. Ito. Boer. and J. 66. B. Phys. G. A. 75. J.” Appl. A. Sun and N. J. “Efficient Tandem Polymer Solar Cells Fabricated by All-Solution Processing. “Improved Efficiency of Photovoltaics Based on CdSe Nanorods and Poly(3Hexylthiophene) Nanofibers. B. 71. 3 Nos. J. J. 80. “Open Circuit Voltage of Stacked Bulk Heterojunction Organic Solar Cells. Coates. Alivisatos. Mater. “Progress in Plastic Electronic Devices. H. “Long-Lived Photoinduced Charge Separation for Solar Cell Applications in Phthalocyanine–Fulleropyrrolidine Dyad Thin Films. 222–225 (2007). 2425–2427 (2002). and S. Rand. 551–554 (2007). Mater. 89 (7). 70. D. V. Mater. P. 1897–1903 (2006). 9.” Appl.” J. Scharber.” Prog.” J. 86 (24).